Materials Letters 61 (2007) 4396 – 4399

www.elsevier.com/locate/matlet

Synthesis and characterization of shaped ZnS nanocrystals in

water in oil microemulsions
Dragana J. Jovanović, Ivana Lj.Validžić, Ivana A. Janković, Nataša Bibić, Jovan M. Nedeljković ⁎
Vinča Institute of Nuclear Sciences, P.O. Box 522, 11001 Belgrade, Serbia
Received 11 January 2007; accepted 9 February 2007
Available online 15 February 2007

Abstract

Shaped zinc sulfide nanocrystals were synthesized in W/O microemulsions by using cyclohexane/Triton X-100/n-pentanol/water system.
Under different synthetic conditions appearance of two distinct morphologies of ZnS nanocrystals, either cubes or nanowires, was proven by
transmission electron microscopy (TEM). The ZnS cubes have an average size of about 25 nm, while the ZnS nanowires have 25 Å diameter and
length ranging from several hundred nanometers up to a few microns. The X-ray diffraction analysis (XRD) revealed formation of ZnS with cubic
zinc blende crystal structure. Due to two dimensional confinement the exciton of ZnS nanowires is blue shifted compared to the bulk material.
Four well-resolved photoluminescence bands in visible spectral region were observed upon excitation of cubic ZnS particles, while in the case of
ZnS nanowires emission band was observed at 421 nm. The origin of photoluminescence bands was discussed in details.
© 2007 Elsevier B.V. All rights reserved.

Keywords: ZnS; Nanowires; Cubes; Nanomaterials; Semiconductors; Microemulsions

1. Introduction systems. Recently, significant influence of temperature [12,13]

The synthesis of nanostructured materials with desired size
and shape has attracted much attention in various fields such as
modern materials, electronics, catalysis, bioimaging, etc. [1–5].
The interest in ZnS nanoparticles (NPs) is justified by their
current and potential application in modern technology due to
their peculiar physicochemical properties [5,6]. Among the
various methods for NPs synthesis, recently usage of water in
oil (W/O) microemulsions as compartmentalized reaction media
has been introduced [7,8]. ZnS NPs have been synthesized
using AOT reversed micelles as nanoreactor [9,10]. Also,
Charinpanitkul et al. [11] synthesized ZnS nanorods with
diameter between 60 and 120 nm coexisting with ZnS
nanospheres in quaternary W/O microemulsion at room
temperature. Xu and Li [12] managed to produce predominantly
uniform ZnS nanorods about 55 nm in diameter with no
presence of cosurfactant. Also, ZnS NWs with diameters around
30 nm [13] as well as diameters in the size range from 40 to
80 nm [14] were reported to be synthesized in reverse micelle
⁎ Corresponding author. Tel.: +381 112458222; fax: +381 112447382.
E-mail address: jovned@vin.bg.ac.yu (J.M. Nedeljković).
0167-577X/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2007.02.012
and ultrasound [15] on the morphology of nanoparticulates
synthesized in complex fluid media has been found. As far as
we are aware the ZnS NWs with a diameter smaller than 5 nm
were reported to be synthesized by other methods [16–21], but
not in W/O microemulsions. Also, no report was found
concerning synthesis of ZnS with cubic morphology.
In this paper, we report synthesis of ZnS NPs with two
distinct morphologies: cubic and wire-like. In both cases
quaternary W/O microemulsions (cyclohexane/Triton X-100/
n-pentanol/water) were used as reaction media, and difference in
morphology was achieved by adjusting reactant concentrations.
The cubic and wire-like ZnS nanoparticulates were character-
ized using structural techniques (TEM and XRD). We found that
the wire-like ZnS particles exhibit size quantization effects due
to two dimensional confinement. The photoluminescence (PL)
property of both kinds of NPs was studied in details.
2. Experimental
All chemicals (zinc chloride, sodium sulfide, cyclohexane,
Triton X-100, n-pentanol, ethanol and toluene) were of the
highest purity available, and they were used without further
 D.J. Jovanović et al. / Materials Letters 61 (2007) 4396–4399
purification. The ZnS nanoparticulates were prepared by rapid
mixing of two separate microemulsions containing ZnCl2 or
Na2S and immediate ultrasound treatment for 15 min. Each
microemulsion contained 0.46 g of n-pentanol, 3.37 g of Triton
X-100, 7.64 g of cyclohexane and 1 g of water, and consequently
the molar ratio between water and surfactant was ω = [H2O]/
[Triton X-100] = 11 in all experiments. Molar ratio between
sulfide and zinc ions was constant ([S2− ]/[Zn2+] = 1), while
concentrations of sulfide and zinc ions were either 0.05 M for
synthesis of ZnS cubes or 0.1 M for synthesis of ZnS NWs.
Sulfide and zinc concentrations were calculated per aqueous
phase. All experiments were performed at 290 K.
In order to perform PL measurements the ZnS nanoparticu-
lates were isolated from microemulsion and transferred to
toluene. Typically, W/O microemulsions containing the ZnS
cubes or the ZnS NWs were destabilized by adding ethanol,
solid being separated by centrifugation and washed with ethanol
four more times using centrifugation in every washing step. The
precipitate was then washed with toluene, the procedure using
centrifugation being repeated four times. Finally, ZnS cubes or
ZnS NWs redispersed in toluene were aged 48 h prior to PL
measurements.
Fig. 1. Typical TEM images of the ZnS cubes (A and B) and the ZnS NWs (C and D) prepared in W/O microemulsion.
4397
Microstructural characterization of ZnS nanoparticulates was
performed by transmission electron microscopy (TEM) using
Philips EM 400 microscope operated at 120 kV. The samples for
TEM measurements were prepared by dissolving one droplet of
microemulsion in 2 ml of ethanol. The obtained samples were
placed on C-coated Cu grids.
The X-ray diffraction (XRD) measurements were carried out
on a BRUKER D8 ADVANCE diffractometer in theta/theta
reflection geometry. Diffraction data for structure analysis were
collected in 2θ range from 10° to 60° with steps of 0.05° and
10 s counting time per step.
Absorption spectra of ZnS were measured using a Perkin
Elmer Lambda 5 UV–VIS Spectrophotometer, while PL spectra
of cleaned ZnS nanoparticulates aged in toluene were recorded
using a Perkin Elmer LS-3B Fluorescence Spectrometer.
3. Results and discussion
The phase behavior of the quaternary microemulsion system
(cyclohexane/Triton X-100/n-pentanol/water) has been described in
details elsewhere [22], and it has been employed successfully in the
synthesis of different kinds of NPs with different morphologies.
4398 D.J. Jovanović et al. / Materials Letters 61 (2007) 4396–4399
Typical TEM images of the ZnS cubes (0.05 M ZnS, [S2−]/[Zn2+] = 1)
and the ZnS NWs (0.1 M ZnS, [S2−]/[Zn2+] = 1) prepared in W/O
microemulsion and aged 48 h are shown in Fig. 1. The ZnS cubes (see
Fig. 1A and B) are in nanometer size domain with an average dimension
of about 25 nm. It should be mentioned that larger as well as smaller ZnS
cubes are also present, but their population is negligible. TEM image of
the sample prepared with higher concentration of reactants (0.1 M ZnS,
[S2−]/[Zn2+] = 1) is shown in Fig. 1C and D.
It can be noticed that the ZnS NWs dominate in the sample,
although some particles with cubic or deformed spherical morphology
are also present. The ZnS NWs have extremely high aspect ratio. The
diameter was estimated to be 25 Å, while the length of the ZnS NWs is
in the range from 750 nm up to a few micrometers. It is important to
emphasize that further increase of the ZnS concentration did not lead to
the formation of exclusively wire-like particles. On the contrary,
deformed cubes and spheres were observed (TEM image not shown).
Under similar experimental conditions (the same reactant concentra-
tion; the same composition of microemulsion; different temperature)
Charinpanitkul et al. [11] synthesized ZnS nanoparticulates. At room
temperature, for lower concentration of reactants (0.05 M) these authors
reported a formation of spherical and rod-shaped ZnS particles, while for
the higher concentration of reactants (0.1 M) exclusive formation of rod-
shaped particles with diameter between 60 and 120 nm was observed. It
seems that in our case small decrease of reaction temperature induced
change of morphology of the ZnS nanoparticulates as well as significant
decrease of their size. This result is in agreement with results obtained by
Xu and Li [12] and Lv et al. [13]. These authors reported a significant
influence of small changes of temperature on the morphology of ZnS
nanoparticulates prepared in microemulsions.
The XRD patterns of the ZnS cubes and the ZnS NWs are shown in
Fig. 2 (curves A and B, respectively). The XRD peaks corresponding to
(1 1 1), (2 2 0) and (3 1 1) lattice planes indicate that synthesized ZnS
NPs with different morphologies (cubes and NWs) are in a cubic phase
(JCPDS No. 5–566). The ZnS XRD peaks are very broad due to the
small crystalline domains in the nanoparticulates. The Debye–Scherrer
diffraction formula was used to estimate the crystalline domain size
(D):
D ¼ kk=bcosh ð1Þ
where k = 0.9 for the ZnS cubic structure, λ = 1.5405 Å is the X-ray
wavelength, β is the full width at half-maximum of the peak and the θ
is the diffraction angle.
Fig. 2. The XRD patterns of the ZnS cubes (A) and the ZnS NWs (B).
Fig. 3. Absorption spectrum of the ZnS NWs (A), as well as PL spectra of the
ZnS NWs (B) and the ZnS cubes (C) (λexc = 300 nm).
The crystalline domain sizes were found to be 30 and 20 Å for the
ZnS cubes and the ZnS NWs, respectively. Having in mind that average
size of ZnS cubes is around 25 nm, it can be concluded that the ZnS
cubes are polycrystalline. On the other hand, the crystalline domain
size of the ZnS NWs is very close to the microscopically estimated
diameter of the ZnS NWs.
Absorption spectrum of the ZnS NWs is shown in Fig. 3 (curve A).
Bulk ZnS with cubic crystal structure has a band gap of 3.6 eV [5] and
consequently absorption onset at 345 nm. It can be noticed that the
position of shoulder that corresponds to the exciton of ZnS NWs is blue
shifted (310 nm) compared to the bulk value due to two dimensional
confinement [19]. This result is in accordance with TEM data (the
diameter of ZnS NWs was found to be 25 Å), since the Bohr diameter of
bulk ZnS is about 5.5 nm [23]. The absorption tail towards visible spectra
region is due to scattering of wire-like ZnS nanocrystals. Much larger
cubic ZnS NPs, off course, do not exhibit size quantization effects and
their absorption spectrum (not shown) corresponds to the bulk material.
The PL spectra of the ZnS NWs and ZnS cubes obtained at room
temperature with 300 nm excitation are also shown in Fig. 3 (curves B
and C, respectively). The PL spectrum of ZnS NWs exhibits a
pronounced peak at 421 nm and shoulders at 452 and 484 nm. The PL
spectrum of ZnS cubes has four well-resolved peaks at 421, 442, 485
and 528 nm. Although different, the PL spectra of ZnS nanoparticulates
have some common features. First, in both cases luminescent peak that
could be assigned to the excitonic emission is lacking [24]. Second, the
observed emission bands in the visible spectral region are the
consequence of the recombination of charge carriers from trap states.
Size dependent excitonic emission band has been observed with
ZnS quantum dots and ZnS nanorods prepared in organic solvents at
high temperatures [19,24]. In the case of ZnS nanoparticulates prepared
at room or lower temperature in aqueous or complex fluid media, due to
much higher extent of crystal lattice imperfection and low level of
surface passivation, the fluorescence usually appears in the visible
spectral region. Most likely the trapped PL originates from sulfur
vacancies [25] and/or surface states [26]. The differences in PL spectra
of ZnS NWs and ZnS cubes are most likely due to different extent of
trap levels associated with different morphologies.
Acknowledgments
The authors are grateful to Dr Miodrag Mitrić for performing
the XRD measurements. Financial support for this study was
 D.J. Jovanović et al. / Materials Letters 61 (2007) 4396–4399 4399

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